Foaming agents, foamable compositions, foams and articles containing fluorine substituted olefins, and methods of making same

ABSTRACT

Various uses of fluoroalkenes, including tetrafluoropropenes, particularly HFO-1234ze, in a variety of applications, including as blowing agents are disclosed.

RELATED APPLICATIONS

The present application is a division of Ser. No. 11/861,803, filed Sep.26, 2007, now U.S. Pat. No. 9,029,430, issued May 12, 2015, whichapplication is related to and claims the priority benefit of U.S.application Ser. No. 11/474,887, now pending, which in turn is relatedto and claims the priority benefit of U.S. Provisional Application No.60/784,731, filed Mar. 21, 2006. U.S. application Ser. No. 11/861,803also is related to and claims the priority benefit of U.S. patentapplication Ser. No. 10/837,525, filed Apr. 29, 2004 now U.S. Pat. No.7,279,451, issued Oct. 9, 2007, which in turn is a continuation-in-partof U.S. patent application Ser. No. 10/694,273, filed Oct. 27, 2003 nowU.S. Pat. No. 4,534,366, issued May 19, 2009, which in turn claims thepriority benefit of U.S. Provisional Application 60/421,263, filed Oct.25, 2002. The disclosure of each of the above is incorporated herein byreference.

FIELD OF THE INVENTION

This invention relates to compositions, methods and systems havingutility in numerous applications, including particularly heat transfersystems such as refrigeration systems. In preferred aspects, the presentinvention is directed to refrigerant compositions which comprise atleast one multi-fluorinated olefin of the present invention.

BACKGROUND

Fluorocarbon based fluids have found widespread use in many commercialand industrial applications, including as aerosol propellants and asblowing agents. Because of certain suspected environmental problems,including the relatively high global warming potentials, associated withthe use of some of the compositions that have heretofore been used inthese applications, it has become increasingly desirable to use fluidshaving low or even zero ozone depletion potential, such ashydrofluorocarbons (“HFCs”). Thus, the use of fluids that do not containsubstantial amounts of chlorofluorocarbons (“CFCs”) orhydrochlorofluorocarbons (“HCFCs”) is desirable. Furthermore, some HFCfluids may have relatively high global warming potentials associatedtherewith, and it is desirable to use hydrofluorocarbon or otherfluorinated fluids having as low global warming potentials as possiblewhile maintaining the desired performance in use properties.Additionally, the use of single component fluids or azeotrope-likemixtures, which do not substantially fractionate on boiling andevaporation, is desirable in certain circumstances.

As suggested above, concern has been increasing in recent years aboutpotential damage to the earth's atmosphere and climate, and certainchlorine-based compounds have been identified as particularlyproblematic in this regard. The use of chlorine-containing compositions(such as chlorofluorocarbons (CFC's), hydrochlorofluorocarbons (HCF's)and the like) as the working fluid in heat transfer systems, such as inrefrigeration and air-conditioning systems, has become disfavoredbecause of the ozone-depleting properties associated with many of suchcompounds. There has thus been an increasing need for new fluorocarbonand hydrofluorocarbon compounds and compositions that are attractivealternatives to the compositions heretofore used in these and otherapplications. For example, it has become desirable to retrofitchlorine-containing systems, such as blowing agent systems orrefrigeration systems, by replacing chlorine-containing compounds withnon-chlorine-containing compounds that will not deplete the ozone layer,such as hydrofluorocarbons (HFC's). Industry in general is continuallyseeking new fluorocarbon based mixtures that offer alternatives to, andare considered environmentally safer substitutes for, CFCs and HCFCs. Itis considered important in many cases, however, that any potentialsubstitute must also possess those properties present in many of themost widely used fluids, such as imparting excellent thermal insulatingproperties and other desirable foam characteristics when used as blowingagents, such as appropriate chemical stability, low- or no-toxicity, lowor no-flammability, among others.

Furthermore, it is generally considered desirably for CFC blowing agentsubstitutes to be effective without major engineering changes toconventional foam generating systems.

Methods and compositions for making conventional foamed materials, suchas for example thermoplastic materials and thermosetting materials, havelong been known. These methods and compositions have typically utilizedchemical and/or physical blowing agents to form the foamed structure ina polymeric matrix. Such blowing agents have included, for example, azocompounds, various volatile organic compounds (VOCs) andchlorofluorocarbons (CFCs). The chemical blowing agents typicallyundergo some form of chemical change, including chemical reaction withthe material that forms the polymer matrix (usually at a predeterminedtemperature/pressure) that causes the release of a gas, such asnitrogen, carbon dioxide, or carbon monoxide. One of the most frequentlyused chemical blowing agents is water. The physical blowing agentstypically are dissolved in the polymer or polymer precursor material andthen expand volumetrically (again at a predeterminedtemperature/pressure) to contribute to the formation of the foamedstructure. Physical blowing agents are frequently used in connectionwith thermoplastic foams, although chemical blowing agents can be usedin place of or in addition to physical blowing agents in connection withthermoplastic foam. For example, it is known to use chemical blowingagent in connection with the formation of polyvinylchloride-based foams.It is common to use chemical blowing and/or physical blowing agents inconnection with thermosetting foams. Of course, it is possible thatcertain compounds and the compositions that contain them may at onceconstitute a chemical and a physical blowing agent.

It was common in the past that the CFCs were used as standard blowingagents in the preparation of isocyanate-based foams, such as rigid andflexible polyurethane and polyisocyanurate foams. For example, CCl₃F(CFC-11) had become a standard blowing agent. However, the use of thismaterial has been banned by international treaty on the grounds that itsrelease into the atmosphere damages the ozone layer in the stratosphere.As a consequence, it is no longer generally common that neat CFC-11 isused as a standard blowing agent for forming thermosetting foams, suchas isocyanate-based foams and phenolic foams.

The problems with CFCs led to the more frequent utilizationhydrogen-containing chlorofluoroalkanes (HCFCs). For example, CHCl₂CF₃(HCFC-123), CH₂ClCHClF (HCFC-141b) have relatively short lifetimes inthe atmosphere. However, while HCFCs are considered to beenvironmentally friendly blowing agents relative to CFCs, such compoundsstill contain some chlorine, and therefore have an “Ozone DepletionPotential” (called “ODP”). Because of the non-zero ODP, HCFCs have beentargeted for eventual removal from use.

Another known class of blowing agents is the non-chlorinated, partiallyhydrogenated fluorocarbons (called “HFCs”). Certain of the HFC currentlybeing used as blowing agents have at least one potentially seriousproblem, namely that they generally have relatively high intrinsicthermal conductivity properties (i.e., poor thermal insulation). On theother hand, foams made with certain of the more modern HFC blowingagents, such as CF₃CH₂CF₂H (“HFC-245fa”) offer improved thermalinsulation, due in part to the low thermal conductivity of HFC-245favapor, and due in part to the fine cell structure HFC-245fa imparts tothe foams. HFC-245fa has been widely used in insulation applications,particularly refrigerator, freezer, refrigerator/freezer and spray foamapplications. Nevertheless, many HFC fluids share the disadvantage ofhaving relatively high global warming potentials, and it is desirable touse hydrofluorocarbon or other fluorinated fluids having as low globalwarming potentials as possible while maintaining the desired performancein use properties. Even the more modern HFCs, such as HFC-245fa,HFC-134a, HFC-365mfc, and others, exhibit a higher than desirable globalwarming potential, albeit low relative to other HFCs. Thus, the use ofHFCs as blowing agents in foam insulation, particularly rigid foaminsulation, has resulted in HFCs being less desirable candidates forblowing agents in commercial foam insulation.

Hydrocarbon blowing agents are also known. For example, U.S. Pat. No.5,182,309 to Hutzen teaches the use of iso- and normal-pentane invarious emulsion mixtures. Another example of hydrocarbon blowing agentsis cyclopentane, as taught by U.S. Pat. No. 5,096,933—Volkert. Althoughmany hydrocarbon blowing agents, such as cyclopentane, and isomers ofpentane, are zero ozone depleting agents and exhibit very low globalwarming potential, such material are less than fully desirable becausefoams produced from these blowing agents lack the same degree of thermalinsulation efficiency as foams made with, for example, HFC-245fa blowingagent. Further, the hydrocarbon blowing agents are extremely flammable,which is undesirable. Also, certain hydrocarbon blowing agents haveinadequate miscibility in certain situations with material from whichthe foam is formed, such as many of the polyester polyols commonly usedin polyisocyanurate modified polyurethane foam. The use of these alkanesfrequently requires a chemical surfactant to obtain a suitable mixture.

There has thus been an increasing need for new compounds andcompositions that are attractive alternatives to the compositionsheretofore used as blowing agents in these and other applications.Applicants have thus recognized a need for new fluorocarbon basedcompounds and compositions that offer effective alternatives to, and areconsidered environmentally safer substitutes for, CFCs and HCFCs. It isgenerally considered highly desirable, however, that any potentialsubstitute must also possess properties, or impart properties to thefoam, that are at least comparable to those associated with many of themost widely used blowing agents, such as vapor phase thermalconductivity (low k-factor), low- or no-toxicity, among others.

One such other potentially important property in many applications isflammability. That is, it is considered either important or essential inmany applications, including particularly in blowing agent applications,to use compositions which are of low flammability or are non-flammable.As used herein, the term “nonflammable” refers to compounds orcompositions which are determined to be nonflammable as determined inaccordance with ASTM standard E-681, dated 2002, which is incorporatedherein by reference. Unfortunately, many HFC's which might otherwise bedesirable for used in refrigerant compositions are not nonflammable. Forexample, the fluoroalkane difluoroethane (HFC-152a) and the fluoroalkene1,1,1-trifluorpropene (HFO-1243zf) are each flammable and therefore notviable for use in many applications.

It has been suggested to use bromine-containing halocarbon additives todecrease flammability of certain materials, including foam blowingagents, in U.S. Pat. No. 5,900,185—Tapscott. The additives in thispatent are said to be characterized by high efficiency and shortatmospheric lifetimes, that is, low ozone depletion potential (ODP) anda low global warming potential (GWP).

While the brominated olefins described in Tapscott may have some levelof effectiveness as anti-flammability agents in connection with certainmaterials, there is no disclosure of the use of such materials as ablowing agent. Furthermore, it is believed that such compounds may alsohave certain disadvantages. For example, applicants have come torecognize that many of the compounds identified in Tapscott will have arelatively low efficiency as a blowing agent due to the relatively highmolecular weight of such compounds. In addition, it is believed thatmany of the compounds disclosed in Tapscott will encounter problems whenused as a blowing agent due to the relatively high boiling point of suchcompounds. Moreover, it is understood by applicants that many compoundswhich have a high level of substitution may possess undesirable toxicityproperties and/or other undesirable properties, such as potentiallyenvironmentally undesirable bioaccumulation.

While Tapscott indicates that bromine-containing alkenes having from 2to 6 carbon atoms may also contain fluorine substituents, this patentappears to suggest that fluorine-containing compounds are less thanfully desirable from the standpoint of environmental safety by notingthat “non-fluorine-containing bromoalkanes will have very shortatmospheric lifetimes due to reaction with tropospheric hydroxyl freeradicals.” (Col. 8, I. 34-39).

Furthermore, it is generally considered desirable for blowing agentsubstitutes to be effective without major engineering changes toconventional equipment and systems used in foam preparation andformation.

Applicants have thus come to appreciate a need for compositions, andparticularly blowing agents, foamable compositions, foamed articles andmethods and systems for forming foam, which provide beneficialproperties and/or avoid one or more of the disadvantages noted above.Applicants have thus come to appreciate a need for compositions, andparticularly blowing agents, that are potentially useful in numerousapplications, while avoiding one or more of the disadvantages notedabove.

This invention relates to compositions, methods and systems havingutility in numerous applications, including particularly in connectionwith compositions, methods, systems and agents relating to polymericfoams.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 provides a sketch of the vessel as discussed in Example 1A.

SUMMARY

Applicants have found that the above-noted need, and other needs, can besatisfied by blowing agent compositions, foamable compositions, foamsand/or foamed articles comprising one or more C2 to C6 fluoroalkenes,more preferably one or more C3 to C5 fluoroalkenes, and even morepreferably one or more compounds having Formula I as follows:

XCF_(z)R₃ _(—) _(z)  (I)

where X is a C1, C2, C3, C4, or C₅ unsaturated, substituted orunsubstituted, radical, each R is independently Cl, F, Br, I or H, and zis 1 to 3, it generally being preferred that the fluoroalkene of thepresent invention has at least four (4) halogen substituents, at leastthree of which are F and even more preferably none of which are Br.

For embodiments in which at least one Br substituent is present, it ispreferred that the compound includes no hydrogen. In such embodiments italso generally preferred that the Br substituent is on an unsaturatedcarbon, and even more preferably the Br substituent is on a non-terminalunsaturated carbon. One particularly preferred compound in this class isCF₃CBr═CF₂, including all of its isomers

In certain embodiments it is highly preferred that the compounds ofFormula I are propenes, butenes, pentenes and hexenes having from 3 to 5fluorine substituents, with other substituents being either present ornot present. In certain preferred embodiments, no R is Br, andpreferably the unsaturated radical contains no Br substituents. Amongthe propenes, tetrafluoropropenes (HFO-1234) and fluorochloroporpenes(such as trifluoro,monochloropropenes (HFCO-1233)), and even morepreferably CF₃CCl═CH₂ (HFO-1233xf) and CF₃CH═CHCl (HFO-1233zd)) areespecially preferred in certain embodiments.

In certain embodiments, pentafluoropropenes are preferred, includingparticularly those pentafluoropropenes in which there is a hydrogensubstituent on the terminal unsaturated carbon, such as CF₃CF═CFH(HFO-1225yez), particularly since applicants have discovered that suchcompounds have a relatively low degree of toxicity in comparison to atleast the compound CF3CH═CF₂(HFO-1225zc).

Among the butenes, fluorochlorobutenes are especially preferred incertain embodiments.

The term “HFO-1234” is used herein to refer to all tetrafluoropropenes.Among the tetrafluoropropenes are included 1,1,1,2-tetrafluoropropene(HFO-1234y1) and both cis- and trans-1,1,1,3-tetrafluoropropene(HFO-1234ze). The term HFO-1234ze is used herein generically to refer to1,1,1,3-tetrafluoropropene, independent of whether it is the cis- ortrans-form. The terms “cisHFO-1234ze” and “transHFO-1234ze” are usedherein to desbribe the cis- and trans-forms of1,1,1,3-tetrafluoropropene respectively. The term “HFO-1234ze” thereforeincludes within its scope cisHFO-1234ze, transHFO-1234ze, and allcombinations and mixtures of these.

The term “HFO-1233” is used herein to refer to alltrifluoro,monochloropropenes. Among the trifluoro,monochloropropenes areincluded 1,1,1,trifluoro-2,chloro-propene (HFCO-1233xf) and both cis-and trans-1,1,1-trifluo-3,chlororopropene (HFCO-1233zd). The termHFCO-1233zd is used herein generically to refer to1,1,1-trifluo-3,chloro-propene, independent of whether it is the cis- ortrans-form. The terms “cisHFCO-1233zd” and “transHFCO-1233zd” are usedherein to describe the cis- and trans-forms of1,1,1-trifluo,3-chlororopropene, respectively. The term “HFCO-1233zd”therefore includes within its scope cisHFCO-1233zd, transHFCO-1233zd,and all combinations and mixtures of these.

The term “HFO-1225” is used herein to refer to all pentafluoropropenes.Among such molecules are included 1,1,1,2,3 pentafluoropropene(HFO-1225yez), both cis- and trans-forms thereof. The term HFO-1225yezis thus used herein generically to refer to 1,1,1,2,3pentafluoropropene, independent of whether it is the cis- or transform.The term “HFO-1225yez” therefore includes within its scopecisHFO-1225yez, transHFO-1225yez, and all combinations and mixtures ofthese. The present invention provides also methods and systems whichutilize the compositions of the present invention, including methods andsystems for foam blowing.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The Compositions

The present compositions can generally be in the form of blowing agentcompositions or foamable compositions. In each case, the presentinvention requires at least one fluoroalkene compound as describedherein and optionally other ingredients, some of which are described indetail below.

A. The Fluoroalkenes

The preferred embodiments of the present invention are directed tocompositions comprising at least one fluoroalkene containing from 2 to6, preferably 3 to 5 carbon atoms, more preferably 3 to 4 carbon atoms,and in certain embodiments most preferably three carbon atoms, and atleast one carbon-carbon double bond. The fluoroalkene compounds of thepresent invention are sometimes referred to herein for the purpose ofconvenience as hydrofluoro-olefins or “HFOs” if they contain at leastone hydrogen. Although it is contemplated that the HFOs of the presentinvention may contain two carbon—carbon double bonds, such compounds atthe present time are not considered to be preferred. For HFOs which alsocontain at least one chlorine atom, the designation HFCO is sometimesused herein

As mentioned above, the present compositions comprise one or morecompounds in accordance with Formula I. In preferred embodiments, thecompositions include one or more compounds of Formula II below:

where each R is independently Cl, F, Br, I or H

R′ is (CR₂)_(n)Y,

Y is CRF₂

and n is 0, 1, 2 or 3, preferably 0 or 1, it being generally preferredhowever that either Br is not present in the compound or when Br ispresent in the compound there is no hydrogen in the compound.

In highly preferred embodiments, Y is CF₃, n is 0 or 1 (most preferably0) and at least one of the remaining Rs is F, and preferably no R is Br,or when Br is present there is no hydrogen in the compound. It ispreferred in certain cases that no R in Formula II is Br.

Applicants believe that, in general, the compounds of the aboveidentified Formulas I and II are generally effective and exhibit utilityin blowing agent compositions in accordance with the teachings containedherein. However, applicants have surprisingly and unexpectedly foundthat certain of the compounds having a structure in accordance with theformulas described above exhibit a highly desirable low level oftoxicity compared to other of such compounds. As can be readilyappreciated, this discovery is of potentially enormous advantage andbenefit for the formulation of blowing agent compositions. Moreparticularly, applicants believe that a relatively low toxicity level isassociated with compounds of Formula I or Formula II (preferably whereinY is CF₃, n is 0 or 1) wherein at least one R on the unsaturatedterminal carbonis H, and at least one of the remaining Rs is F or Cl. Applicantsbelieve also that all structural, geometric and stereoisomers of suchcompounds are effective and of beneficially low toxicity.

In certain preferred embodiments, the compound of the present inventioncomprises a C3 or C4 HFO or HFCO, preferably a C3 HFO, and morepreferably a compound in accordance with Formula I in which X is ahalogen substituted C3 alkylene and z is 3. In certain of suchembodiments X is fluorine and/or chlorine substituted C3 alkylene, withthe following C3 alkylene radicals being preferred in certainembodiments:

-   -   —CH═CF—CH₃    -   —CF═CH—CH₃    -   —CH₂—CF═CH₂    -   —CH₂—CH═CFH,        Such embodiments therefore comprise the following preferred        compounds: CF₃—CH═CF—CH₃; CF₃—CF═CH—CH₃; CF₃—CH₂—CF═CH₂;        CF₃—CH₂—CH═CFH; and combinations of these with one another        and/or with other compounds in accordance with Formula I or        Formula II.

In certain preferred embodiments, the compound of the present inventioncomprises a C3 or C4 HFCO, preferably a C3 HFCO, and more preferably acompound in accordance with Formula II in which Y is CF₃, n is 0, atleast one R on the unsaturated terminal carbon is H, and at least one ofthe remaining Rs is Cl. HFCO-1233 is an example of such a preferredcompound.

In highly preferred embodiments, especially embodiments which comprisethe low toxicity compounds described above, n is zero. In certain highlypreferred embodiments the compositions of the present invention compriseone or more tetrafluoropropenes, including HFO-1234yf, (cis)HFO-1234zeand (trans)HFO-1234ze, with HFO-1234ze being generally preferred andtrans HFO-1234ze being highly preferred in certain embodiments. Althoughthe properties of (cis)HFO-1234ze and (trans)HFO-1234ze differ in atleast some respects, it is contemplated that each of these compounds isadaptable for use, either alone or together with other compoundsincluding its stereo isomer, in connection with each of theapplications, methods and systems described herein. For example,(trans)HFO-1234ze may be preferred for use in certain systems because ofits relatively low boiling point (−19° C.), while (cis)HFO-1234ze, witha boiling point of +9° C., may be preferred in other applications. Ofcourse, it is likely that combinations of the cis- and trans-isomerswill be acceptable and/or preferred in many embodiments. Accordingly, itis to be understood that the terms “HFO-1234ze” and1,3,3,3-tetrafluoropropene refer to both stereo isomers, and the use ofthis term is intended to indicate that each of the cis- and trans-formsapplies and/or is useful for the stated purpose unless otherwiseindicated.

HFO-1234 compounds are known materials and are listed in ChemicalAbstracts databases. The production of fluoropropenes such as CF₃CH═CH₂by catalytic vapor phase fluorination of various saturated andunsaturated halogen-containing C3 compounds is described in U.S. Pat.Nos. 2,889,379; 4,798,818 and 4,465,786, each of which is incorporatedherein by reference. EP 974,571, also incorporated herein by reference,discloses the preparation of 1,1,1,3-tetrafluoropropene by contacting1,1,1,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with achromium-based catalyst at elevated temperature, or in the liquid phasewith an alcoholic solution of KOH, NaOH, Ca(OH)₂ or Mg(OH)₂. Inaddition, methods for producing compounds in accordance with the presentinvention are described generally in connection with pending UnitedStates patent application entitled “Process for Producing Fluorpropenes”U.S. application Ser. No. 10/694,272, not U.S. Pat. No. 7,230,146, whichis also incorporated herein by reference.

Other preferred compounds for use in accordance with the presentinvention include pentafluoropropenes, including all isomers thereof(eg., HFO-1225), tetra- and penta-fluorobutenes, including all isomersthereof (eg., HFO-1354 and HFO-1345). Of course, the presentcompositions may comprise combinations of any two or more compoundswithin the broad scope of the invention or within any preferred scope ofthe invention.

The present compositions, particularly those comprising HFO-1234(including HFO-1234ze and HFO-1234yf), are believed to possessproperties that are advantageous for a number of important reasons. Forexample, applicants believe, based at least in part on mathematicalmodeling, that the fluoroolefins of the present invention will not havea substantial negative affect on atmospheric chemistry, being negligiblecontributors to ozone depletion in comparison to some other halogenatedspecies. The preferred compositions of the present invention thus havethe advantage of not contributing substantially to ozone depletion. Thepreferred compositions also do not contribute substantially to globalwarming compared to many of the hydrofluoroalkanes presently in use.

In certain preferred forms, compositions of the present invention have aGlobal Warming Potential (GWP) of not greater than about 1000, morepreferably not greater than about 500, and even more preferably notgreater than about 150. In certain embodiments, the GWP of the presentcompositions is not greater than about 100 and even more preferably notgreater than about 75. As used herein, “GWP” is measured relative tothat of carbon dioxide and over a 100 year time horizon, as defined in“The Scientific Assessment of Ozone Depletion, 2002, a report of theWorld Meteorological Association's Global Ozone Research and MonitoringProject,” which is incorporated herein by reference.

In certain preferred forms, the present compositions also preferablyhave an Ozone Depletion Potential (ODP) of not greater than 0.05, morepreferably not greater than 0.02 and even more preferably about zero. Asused herein, “ODP” is as defined in “The Scientific Assessment of OzoneDepletion, 2002, A report of the World Meteorological Association'sGlobal Ozone Research and Monitoring Project,” which is incorporatedherein by reference.

The amount of the Formula I compounds, particularly HFO-1234 and evenmore preferably HFO-1234ze, contained in the present compositions canvary widely, depending the particular application, and compositionscontaining more than trace amounts and less than 100% of the compoundare within broad the scope of the present invention. Moreover, thecompositions of the present invention can be azeotropic, azeotrope-likeor non-azeotropic. In preferred embodiments, the present compositions,particularly blowing agent compositions, comprise Formula I and/orFormula II compounds, preferably HFO-1234 and more preferably HFO-1234zeand/or HFO-1234yf, in amounts from about 1% by weight to about 99% byweight, more preferably from about 5% to about 95% by weight, and evenmore preferably from 40% to about 90%. by wieght.

B. Other Components—Blowing Agent Compositions

It is contemplated that in certain embodiments of the present inventionthe blowing agent compositions consist of or consist essentially of oneor more compounds in accordance with Formula I hereof. Thus, the presentinvention includes methods and systems which include using one or moreof the compounds of the present invention as a blowing agent without thepresence of any substantial amount of additional components. However,one or more compounds or components that are not within the scope ofFormula I or Formula II are optionally, but preferably, included in theblowing agent compositions of the present invention. Such optionaladditional compounds include, but are not limited to, other compoundswhich also act as blowing agents (hereinafter referred to forconvenience but not by way of limitation as co-blowing agents),surfactants, polymer modifiers, toughening agents, colorants, dyes,solubility enhancers, rheology modifiers, plasticizing agents,flammability suppressants, antibacterial agents, viscosity reductionmodifiers, fillers, vapor pressure modifiers, nucleating agents,catalysts and the like. In certain preferred embodiments, dispersingagents, cell stabilizers, surfactants and other additives may also beincorporated into the blowing agent compositions of the presentinvention. Certain surfactants are optionally but preferably added toserve as cell stabilizers. Some representative materials are sold underthe names of DC-193, B-8404, and L-5340 which are, generally,polysiloxane polyoxyalkylene block co-polymers such as those disclosedin U.S. Pat. Nos. 2,834,748, 2,917,480, and 2,846,458, each of which isincorporated herein by reference. Other optional additives for theblowing agent mixture may include flame retardants such astri(2-chloroethyl)phosphate, tri(2-chloropropyl)phosphate,tri(2,3-dibromopropyl)-phosphate, tri(1,3-dichloropropyl)phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminum trihydrate, polyvinyl chloride, and the like.

With respect to nucleating agents, all known compounds and materialshaving nucleating functionality are available for use in the presentinvention, including particularly talc.

Of course other compounds and/or components that modulate a particularproperty of the compositions (such as cost for example) may also beincluded in the present compositions, and the presence of all suchcompounds and components is within the broad scope of the invention.

Thus, the preferred embodiments of the present compositions include, inaddition to the compounds of Formula I (including particularlyHFO-1234ze and/or HFO-1234y1), one or more co-blowing agents. Theco-blowing agent in accordance with the present invention can comprise aphysical blowing agent, a chemical blowing agent (which preferably incertain embodiments comprises water) or a blowing agent having acombination of physical and chemical blowing agent properties. It willalso be appreciated that the blowing agents included in the presentcompositions, including the compounds of Formula I as well as theco-blowing agent, may exhibit properties in addition to those requiredto be characterized as a blowing agent. For example, it is contemplatedthat the blowing agent compositions of the present invention may includecomponents, including the compounds or Formula I described above, whichalso impart some beneficial property to the blowing agent composition orto the foamable composition to which it is added. For example, it iswithin the scope of the present invention for the compound of Formula Ior for the co-blowing agent to also act as a polymer modifier or as aviscosity reduction modifier.

Although it is contemplated that a wide range of co-blowing agents maybe used in accordance with the present invention, in certain embodimentsit is preferred that the blowing agent compositions of the presentinvention include one or more HFCs as co-blowing agents, more preferablyone or more C1-C4 HFCs, and/or one or more hydrocarbons, more preferablyC4-C6 hydrocarbons. For example, with respect to HFCs, the presentblowing agent compositions may include one or more of difluoromethane(HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152),trifluoroethane (HFC-143), tetrafluoroethane (HFC-134),pentafluoroethane (HFC-125), pentafluoropropane (HFC-245),hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea),pentafluorobutane (HFC-365), hexafluorobutane (HFC-356) and all isomersof all. such HFC's. With respect to hydrocarbons, the present blowingagent compositions may include in certain preferred embodiments, forexample, iso, normal and/or cyclopentane for thermoset foams and butaneor isobutane for thermoplastic foams. Of course other materials, such aswater, CO₂, CFCs (such as trichlorofluoromethane (CFC-11) anddichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs such asdichloroethylene (preferably trans-dichloroethylene), ethyl chloride andchloropropane), HCFCs, CI-C5 alcohols (such as, for example, ethanoland/or propanol and/or butanol), CI-C4 aldehydes, CI-C4 ketones, CI-C4ethers (including ethers (such as dimethyl ether and diethyl ether),diethers (such as dimethoxy methane and diethoxy methane)), and methylformate including combinations of any of these may be included, althoughsuch components are contemplated to be not preferred in many embodimentsdue to negative environmental impact.

In certain embodiments, one or more of the following HFC isomers arepreferred for use as co-blowing agents in the compositions of thepresent invention:

-   1,1,1,2,2-pentafluoroethane (HFC-125)-   1,1,2,2-tetrafluoroethane (HFC-134)-   1,1,1,2-tetrafluoroethane (HFC-134a)-   1,1-difluoroethane (HFC-152a)-   1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea)-   1,1,1,3,3,3-hexafluoropropane (HFC-236fa)-   1,1,1,3,3-pentafluoropropane (HFC-245fa) and-   1,1,1,3,3-pentafluorobutane (HFC-365mfc).

The relative amount of any of the above noted additional co-blowingagents, as well as any additional components which may be included inpresent compositions, can vary widely within the general broad scope ofthe present invention according to the particular application for thecomposition, and all such relative amounts are considered to be withinthe scope hereof. Applicants note, however, that one particularadvantage of at least certain of the compounds of Formula I inaccordance with the present invention, for example HFO-1234ze, is therelatively low flammability of such compounds. Accordingly, in certainembodiments it is preferred that the blowing agent composition of thepresent invention comprise at least one co-blowing agent and an amountof compound(s) in accordance with Formula I sufficient to produce ablowing agent composition which is overall nonflammable. Thus, in suchembodiments, the relative amounts of the co-blowing agent in comparisonto the compound of Formula I will depend, at least in part, upon theflammability of the co-blowing agent.

The blowing agent compositions of the present invention may include thecompounds of the present invention in widely ranging amounts. It isgenerally preferred, however, that for preferred compositions for use asblowing agents in accordance with the present invention, compound(s) inaccordance with Formula I, and even more preferably Formula II, arepresent in an amount that is at least about 1% by weight, morepreferably at least about 5% by weight, and even more preferably atleast about 15% by weight, of the composition. In certain preferredembodiments, the blowing agent comprises at least about 50% by weight ofthe present blowing agent compound(s), and in certain embodiments theblowing agent consists essentially of compounds in accordance with thepresent invention. In this regard it is noted that the use of one ormore co-blowing agents is consistent with the novel and basic featuresof the present invention. For example, it is contemplated that waterwill be used as either a co-blowing or in combination with otherco-blowing agents (such as, for example, pentane, particularlycyclopentane) in a large number of embodiments.

It is contemplated that the blowing agent compositions of the presentinvention may comprise, preferably in amounts of at least about 15% byweight of the composition, HFO-1234yf, cisHFO-1234ze, transHFO1234ze orcombinations of two or more of these. In many preferred embodiments, aco-blowing agent comprising water is included in the compositions, mostpreferably in compositions directed to the use of thermosetting foams.In certain preferred embodiments, the blowing agent compositions of thepresent invention comprise a combination of cisHFO-1234ze andtransHF01234ze in a cis:trans weight ratio of from about 1:99 to about50:50, more preferably from about 10:90 to about 30:70. In certainembodiments, it may be preferred to use a combination of cisHFO-1234zeand transHF01234ze in a cis:trans weight ratio of from about 1:99 toabout 10:90, and preferably from about 1:99 to about 5:95. Of course, itmay be desirable in certain embodiments to use combinations in which thecis-isomer is present in a higher concentration than the trans-isomer,as may be the case, for example, for use with foamable compositionsadapted for use with liquid blowing agents.

In certain preferred embodiments, the blowing agent compositioncomprises from about 30% to about 95% by weight of a compound of FormulaI, more preferably a compound of Formula II, and even more preferablyone or more HFO-1234 compounds, and from about 5% to about 90% byweight, more preferably from about 5% to about 65% by weight ofco-blowing agent. In certain of such embodiments the co-blowing agentcomprises, and preferably consists essentially of, H₂O, HFCs,hydrocarbons, alcohols (preferably C2, C3 and/or C4 alcohols), CO₂, andcombinations of these. In preferred embodiments in which the co-blowingagent comprises H₂O, the composition comprises H₂O in an amount of fromabout 5% by weight to about 50% by weight of the total blowing agentcomposition, more preferably from about 10% by weight to about 40% byweight, and even more preferably of from about 10% to about 20% byweight of the total blowing agent.

In preferred embodiments in which the co-blowing agent comprises CO2,the composition comprises CO₂ in an amount of from about 5% by weight toabout 60% by weight of the total blowing agent composition, morepreferably from about 20% by weight to about 50% by weight, and evenmore preferably of from about 40% to about 50% by weight of the totalblowing agent.

In preferred embodiments in which the co-blowing agent comprisesalcohols, (preferably C2, C3 and/or C4 alcohols), the compositioncomprises alcohol in an amount of from about 5% by weight to about 40%by weight of the total blowing agent composition, more preferably fromabout 10% by weight to about 40% by weight, and even more preferably offrom about 15% to about 25% by weight of the total blowing agent.

For compositions which include HFC co-blowing agents, the HFC co-blowingagent (preferably C2, C3, C4 and/or C5 HFC), and even more preferablydifluoromethane (HFC-152a) (HFC-152a being particularly preferred forextruded thermoplastics) and/or pentafluoropropane (HFC-245)), ispreferably present in the composition in amounts of from of from about5% by weight to about 80% by weight of the total blowing agentcomposition, more preferably from about 10% by weight to about 75% byweight, and even more preferably of from about 25% to about 75% byweight of the total blowing agent. Furthermore, in such embodiments, theHFC is preferably C2-C4 HFC, and even more preferably C3 HFC, withpenta-fluorinated C3 HFC, such as HFC-245fa, being highly preferred incertain embodiments.

For compositions which include HC co-blowing agents, the HC co-blowingagent (preferably C3, C4 and/or C5 HC) is preferably present in thecomposition in amounts of from of from about 5% by weight to about 80%by weight of the total blowing agent composition, and even morepreferably from about 20% by weight to about 60% by weight of the totalblowing agent.

C. Other Components—Foamable Compositions

One aspect of the present invention provides foamable compositions. Asis known to those skilled in the art, foamable compositions generallyinclude one or more components capable of forming foam. As used herein,the term “foam foaming agent” is used to refer to a component, or acombination on components, which are capable of forming a foamstructure, preferably a generally cellular foam structure. The foamablecompositions of the present invention include such component(s) and ablowing agent compound, preferably a compound of Formula I, inaccordance with the present invention. In certain embodiments, the oneor more components capable of forming foam comprise a thermosettingcomposition capable of forming foam and/or foamable compositions.Examples of thermosetting compositions include polyurethane andpolyisocyanurate foam compositions, and also phenolic foam compositions.This reaction and foaming process may be enhanced through the use ofvarious additives such as catalysts and surfactant materials that serveto control and adjust cell size and to stabilize the foam structureduring formation. Furthermore, is contemplated that any one or more ofthe additional components described above with respect to the blowingagent compositions of the present invention could be incorporated intothe foamable composition of the present invention. In such thermosettingfoam embodiments, one ormore of the present compositions are included asor part of a blowing agent in a foamable composition, or as a part of atwo or more part foamable composition, which preferably includes one ormore of the components capable of reacting and/or foaming under theproper conditions to form a foam or cellular structure.

In certain other embodiments of the present invention, the one or morecomponents capable of foaming comprise thermoplastic materials,particularly thermoplastic polymers and/or resins. Examples ofthermoplastic foam components include polyolefins, such as for examplemonovinyl aromatic compounds of the formula Ar—CHCH2 wherein Ar is anaromatic hydrocarbon radical of the benzene series such as polystyrene(PS). Other examples of suitable polyolefin resins in accordance withthe invention include the various ethylene resins including the ethylenehomopolymers such as polyethylene and ethylene copolymers, polypropylene(PP) and polyethyleneterepthalate (PET). In certain embodiments, thethermoplastic foamable composition is an extrudable composition.

Methods and Systems

It is contemplated that all presently known and available methods andsystems for forming foam are readily adaptable for use in connectionwith the present invention. For example, the methods of the presentinvention generally require incorporating a blowing agent in accordancewith the present invention into a foamable or foam forming compositionand then foaming the composition, preferably by a step or series ofsteps which include causing volumetric expansion of the blowing agent inaccordance with the present invention. In general, it is contemplatedthat the presently used systems and devices for incorporation of blowingagent and for foaming are readily adaptable for use in accordance withthe present invention. In fact, it is believed that one advantage of thepresent invention is the provision of an improved blowing agent which isgenerally compatible with existing foaming methods and systems.

Thus, it will be appreciated by those skilled in the art that thepresent invention comprises methods and systems for foaming all types offoams, including thermosetting foams, thermoplastic foams andformed-in-place foams. Thus, one aspect of the present invention is theuse of the present blowing agents in connection conventional foamingequipment, such as polyurethane foaming equipment, at conventionalprocessing conditions. The present methods therefore include masterbatchtype operations, blending type operations, third stream blowing agentaddition, and blowing agent addition at the foam head.

With respect to thermoplastic foams, the preferred methods generallycomprise introducing a blowing agent in accordance with the presentinvention into a thermoplastic material, preferably thermoplasticpolymer such as polyolefin, and then subjecting the thermoplasticmaterial to conditions effective to cause foaming. For example, the stepof introducing the blowing agent into the thermoplastic material maycomprise introducing the blowing agent into a screw extruder containingthe thermoplastic, and the step of causing foaming may comprise loweringthe pressure on the thermoplastic material and thereby causing expansionof the blowing agent and contributing to the foaming of the material.

It will be appreciated by those skilled in the art, especially in viewof the disclosure contained herein, that the order and manner in whichthe blowing agent of the present invention is formed and/or added to thefoamable composition does not generally affect the operability of thepresent invention. For example, in the case of extrudable foams, it ispossible that the various components of the blowing agent, and even thecomponents of the foamable composition, be not be mixed in advance ofintroduction to the extrusion equipment, or even that the components arenot added to the same location in the extrusion equipment. Moreover, theblowing agent can beintroduced either directly or as part of a premix,which is then further added to other parts of the foamable composition.

Thus, in certain embodiments it may be desired to introduce one or morecomponents of the blowing agent at first location in the extruder, whichis upstream of the place of addition of one or more other components ofthe blowing agent, with the expectation that the components will cometogether in the extruder and/or operate more effectively in this manner.Nevertheless, in certain embodiments, two or more components of theblowing agent are combined in advance and introduced together into thefoamable composition, either directly or as part of premix which is thenfurther added to other parts of the foamable composition.

One embodiment of the present invention relates to methods of formingfoams, and preferably polyurethane and polyisocyanurate foams. Themethods generally comprise providing a blowing agent composition of thepresent inventions, adding (directly or indirectly) the blowing agentcomposition to a foamable composition, and reacting the foamablecomposition under the conditions effective to form a foam or cellularstructure, as is well known in the art. Any of the methods well known inthe art, such as those described in “Polyurethanes Chemistry andTechnology,” Volumes I and II, Saunders and Frisch, 1962, John Wiley andSons, New York, N.Y., which is incorporated herein by reference, may beused or adapted for use in accordance with the foam embodiments of thepresent invention. In general, such preferred methods comprise preparingpolyurethane or polyisocyanurate foams by combining an isocyanate, apolyol or mixture of polyols, a blowing agent or mixture of blowingagents comprising one or more of the present compositions, and othermaterials such as catalysts, surfactants, and optionally, flameretardants, colorants, or other additives. It is convenient in manyapplications to provide the components for polyurethane orpolyisocyanurate foams in pre-blended formulations. Most typically, thefoam formulation is pre-blended into two components. The isocyanate andoptionally certain surfactants and blowing agents comprise the firstcomponent, commonly referred to as the “A” component. The polyol orpolyol mixture, surfactant, catalysts, blowing agents, flame retardant,and other isocyanate reactive components comprise the second component,commonly referred to as the “B” component. Accordingly, polyurethane orpolyisocyanurate foams are readily prepared by bringing together the Aand B side components either by hand mix for small preparations and,preferably, machine mix techniques to form blocks, slabs, laminates,pour-in-place panels and other items, spray applied foams, froths, andthe like. Optionally, other ingredients such as fire retardants,colorants, auxiliary blowing agents, and even other polyols can be addedas one or more additional streams to the mix head or reaction site. Mostpreferably, however, they are all incorporated into one B-component asdescribed above.

The present methods and systems also include forming a one componentfoam, preferably polyurethane foam, containing a blowing agent inaccordance with the present invention. In certain preferablyembodiments, a portion of the the blowing agent is contained in the foamforming agent, preferably by being dissolved in a foam forming agentwhich is liquid at the pressure within the container, a second portionof the blowing agent is present as a separate gas phase. In suchsystems, the contained/dissolved blowing agent performs, in large part,to cause the expansion of the foam, and the separate gas phase operatesto impart propulsive force to the foam forming agent. Such one componentsystems are typically and preferably packaged in a container, such as anaerosol type can, and the blowing agent of the present invention thuspreferably provides for expansion of the foam and/or the energy totransport the foam/foamable material from the package, and preferablyboth. In certain embodiments, such systems and methods comprise chargingthe package with a fully formulated system (preferably isocyanate/polyolsystem) and incorporating a gaseous blowing agent in accordance with thepresent invention into the package, preferably an aerosol type can.

Any of the methods well known in the art, such as those described in“Polyurethanes Chemistry and Technology,” Volumes I and II, Saunders andFrisch, 1962, John Wiley and Sons, New York, N.Y., which is incorporatedherein by reference, may be used or adapted for use in accordance withthe foam forming embodiments of the present invention. It iscontemplated also that in certain embodiments it may be desirable toutilize the present compositions when in the supercritical or nearsupercritical state as a blowing agent.

The Foams

The invention also relates to all foams, (including but not limited toclosed cell foam, open cell foam, rigid foam, flexible foam, integralskin and the like) prepared from a polymer foam formulation containing ablowing agent comprising the compositions of the invention. Applicantshave found that one advantage of the foams, and particularly thermosetfoams such as polyurethane foams, in accordance with the presentinvention is the ability to achieve, preferably in connection withthermoset foam embodiments, exceptional thermal performance, such as canbe measured by the K-factor

or lambda, particularly and preferably under low temperature conditions.Although it is contemplated that the present foams, particularlythermoset foams of the present invention, may be used in a wide varietyof applications, in certain preferred embodiments the present inventioncomprises appliance foams in accordance with the present invention,including refrigerator foams, freezer foams, refrigerator/freezer foams,panel foams, and other cold or cryogenic manufacturing applications.

The foams in accordance with the present invention, in certain preferredembodiments, provide one or more exceptional features, characteristicsand/or properties, including: thermal insulation efficiency(particularly for thermoset foams), dimensional stability, compressivestrength, aging of thermal insulation properties, all in addition to thelow ozone depletion potential and low global warming potentialassociated with many of the preferred blowing agents of the presentinvention. In certain highly preferred embodiments, the presentinvention provides thermoset foam, including such foam formed into foamarticles, which exhibit improved thermal conductivity relative to foamsmade using the same blowing agent (or a commonly used blowing agentHFC-245fa) in the same amount but without the compound of Formula I inaccordance with the present invention. In certain highly preferredembodiments, the thermoset foams, and preferably polyurethane foams, ofthe present invention exhibit a K-factor (BTU in/hr ft²° F.) at 40° F.of not greater than about 0.14, more preferably not greater than 0.135,and even more preferably not greater than 0.13. Furthermore, in certainembodiments, it is preferred that the thermoset foams, and preferablythe polyurethane foams of the present invention exhibit a K-factor (BTUin/hr ft²° F.) at 75° F. of not greater than about 0.16, more preferablynot greater than 0.15, and even more preferably not greater than 0.145.In other preferred embodiments, the present foams exhibit improvedmechanical properties relative to foams produced with blowing agentsoutside the scope of the present invention. For example, certainpreferred embodiments of the present invention provide foams and foamarticles having a compressive strength which is superior to, andpreferably at least about 10 relative percent, and even more preferablyat least about 15 relative percent greater than a foam produced undersubstantially identical conditions by utilizing a blowing agentconsisting of cyclopentane. Furthermore, it is preferred in certainembodiments that the foams produced in accordance with the presentinvention have compressive strengths that are on a commercial basiscomparable to the compressive strength produced by making a foam undersubstantially the same conditions except wherein the blowing agentconsists of HFC-245fa. In certain preferred embodiments, the foams ofthe present invention exhibit a compressive strength of at least about12.5% yield (in the parallel and perpendicular directions), and evenmore preferably at least about 13% yield in each of said directions.

EXAMPLES

The following examples are provided for the purpose of illustrating thepresent invention but without limiting the scope thereof.

Example 1A Polystyrene Foam

This example illustrates the use of blowing agent in accordance with twopreferred embodiments of the present invention, namely the use ofHFO-1234ze and HFO-1234yf, and the production of polystyrene foam. Atesting apparatus and protocol has been established as an aid todetermining whether a specific blowing agent and polymer are capable ofproducing a foam and the quality of the foam. Ground polymer (DowPolystyrene 685D) and blowing agent consisting essentially of HFO-1234zeare combined in a vessel (FIG. 1). The vessel volume is 200 cm³ and itis made from two pipe flanges and a section of 2-inch diameter schedule40 stainless steel pipe 4 inches long. The vessel is placed in an oven,with temperature set at from about 190° F. to about 285° F., preferablyfor polystyrene at 265° F., and remains there until temperatureequilibrium is reached. The pressure in the vessel is then released,quickly producing a foamed polymer. The blowing agent plasticizes thepolymer as it dissolves into it. The resulting density of the two foamsthus produced using this method are given in Table 1 as the density ofthe foams produced using trans-HFO-1234ze and HFO-1234yf. The data showthat foam polystyrene is obtainable in accordance with the presentinvention. In this regard it is noted that the bulk density ofpolystyrene is 1050 kg/m³ or 65.625 lb/ft³ at about room temperature.

TABLE 1 Dow polystyrene 685D Foam density (lb/ft³) (at room temperature)Foam Formation Temperature, ° F. HFO-1234yf 275 55.15 260 22.14 14.27250 7.28 24.17 240 16.93

Example 1B Polystyrene Foam

This example demonstrates the performance of HFO-1234ze alone as ablowing agent for polystyrene foam formed in a twin screw type extruder.The apparatus employed in this example is a Leistritz twin screwextruder having the following characteristics:

-   -   5        30 mm co-rotating screws

L:D Ratio=40:1

The extruder is divided into 10 sections, each representing a L:D of4:1. The polystyrene resin was introduced into the first section, theblowing agent was introduced into the sixth section, with the extrudateexiting the tenth section. The extruder operated primarily as amelt/mixing extruder. A subsequent cooling extruder is connected intandem, for which the design characteristics were:

Leistritz twin screw extruder

40 mm co-rotating screws

L:D Ratio=40:1

Die: 5.0 mm circular

Polystyrene resin, namely Nova Chemical—general extrusion gradepolystyrene, identified as Nova 1600, is feed to the extruder under theconditions indicated above. The resin has a recommended melt temperatureof 375° F.-525° F. The pressure of the extruder at the die is about 1320pounds per square inch (psi), and the temperature at the die is about115° C.

A blowing agent consisting essentially of transHFO-1234ze is added tothe extruder at the location indicated above, with about 0.5% by weightof talc being included, on the basis of the total blowing agent, as anucleating agent. Foam is produced using the blowing agent atconcentrations of 10% by weight, 12% by weight, and 14% by weight, inaccordance with the present invention. The density of the foam producedis in the range of about 0.1 grams per cubic centimeter to 0.07 gramsper cubic centimeter, with a cell size of about 49 to about 68 microns.The foams, of approximately 30 millimeters diameter, are visually ofvery good quality, very fine cell size, with no visible or apparent blowholes or voids.

Example 1C Polystyrene Foam

This procedure of Example 1B is repeated except that the foaming agentcomprises about 50% by weight transHFO-1234ze and 50% by weight ofHFC-245fa and nucleating agent in the concentration indicated in Example1B. Foamed polystyrene is prepared at blowing agent concentrations ofapproximately 10% and 12%. The density of the foam produced is about0.09 grams per cubic centimeter, with a cell size of about 200 microns.The foams, of approximately 30 millimeters diameter, are visually ofvery good quality, fine cell structure, with no visible or apparentvoids.

Example 1D Polystyrene Foam

This procedure of Example 1B is repeated except that the foaming agentcomprises about 80% by weight HFO-1234ze and 20% by weight of HFC-245faand nucleating agent in the concentration indicated in Example 1B.Foamed polystyrene is prepared at blowing agent concentrations ofapproximately 10% and 12%. The density of the foam produced is about0.08 grams per cubic centimeter, with a cell size of about 120 microns.The foams, of approximately 30 millimeters diameter, are visually ofvery good quality, fine cell structure, with no visible or apparentvoids.

Example IE Polystyrene Foam

This procedure of Example 1B is repeated except that the foaming agentcomprises about 80% by weight HFO-124ze and 20% by weight of HFC-245faand nucleating agent in the concentration indicated in Example 1B.Foamed polystyrene is prepared at blowing agent concentrations ofapproximately 10% and 12%. The foams' density was in the range of 0.1grams per cubic centimeter, and. The foams, of approximately 30millimeters diameter, are visually of very good quality, fine cellstructure, with no visible or apparent voids.

Example 1F Polystyrene Foam

This procedure of Example 1E is repeated except that the nucleatingagent is omitted. The foams' density was in the range of 0.1 grams percubic centimeter, and the cell size diameter is about 400. The foams, ofapproximately 30 millimeters diameter, are visually of very goodquality, fine cell structure, with no visible or apparent voids.

Example 2 Polyurethane Foam Compressive Strength

This example demonstrates the performance of HFO-1234ze, and isomersthereof, used in combination with hydrocarbon co-blowing agents, and inparticular the utility of compositions comprising HFO-1234ze andcyclopentane co-blowing agents in compressive strength performance ofpolyurethane foams.

A commercially available, refrigeration appliance-type polyurethane foamformulation (foam forming agent) is provided. The polyol blend consistedof commercial polyol(s), catalyst(s), and surfactant(s). Thisformulation is adapted for use in connection with a gaseous blowingagent. Standard commercial polyurethane processing equipment is used forthe foam forming process. A gaseous blowing agent combination was formedcomprising HFO-1234ze (including isomers thereof) in a concentration ofapproximately 60 mole percent, and cyclopentane in a concentration ofapproximately 40 mole percent of the total blowing agent. This exampleillustrates the physical property performance of combinations ofHFO-1234ze (including isomers thereof) in combination with cyclopentaneco-blowing agent. Table 2 below reports the compressive strength ofsimilar machine-made polyurethane foams using a blowing agent of thepresent invention in comparison to foams made using a blowing agentconsisting of HFC-245fa and a blowing agent consisting of cyclopentane.

TABLE 2 Compressive Strength Parallel Perpendicular Blowing Agent %Yield % Yield HF01234ze/tycyclopentane 13.513 14.672 HFC-245fa 13.88114.994 Cyclopentane 11.462 10.559

One unexpected result illustrated by this example is the ability toprocess HFO-1234ze, and HFC-1234ze/HFC blends in conventional foamprocessing equipment, and polyurethane processing equipment inparticular. This is potentially of a great advantage in so far that itpermits foam processing with various types of systems and equipment,including: masterbatch type blending equipment, gaseous blowing agentblending equipment, third stream addition of the blowing agent, orblowing agent addition at the foam head.

Example 3 Polyurethane Foam K-Factors

A polyurethane foam is prepared and is adapted for use as a commercial“appliance type” polyurethane formulation. The same foam formulationdescribed in Example 2 is used in connection with the same standardcommercial polyurethane processing equipment is used in the foam formingprocess. Several systems are prepared, with each system using identicalcomponents, systems, and equipment, with the exception of the blowingagent. In addition to blowing agent in accordance with the presentinvention, HFC-134a, HFC-245fa, and cyclopentane are each also tested asthe blowing agent. In each system, the blowing agent is added insubstantially the same molar concentration into the polyol blend. Thepolyol blend consists of commercial polyol(s), catalyst(s), andsurfactant(s). The foams are prepared in accordance with standardcommercial manufacturing operations, for example a commercial operationfor making foam for refrigeration applications. The prepared foams wereevaluated for k-5 factor, and this information is reported below inTable 3. For benchmark, comparative purposes, foams were prepared withHFC-134a, for which commercial data can be referenced. The k-factor datafor these foams are shown in Table 3.

TABLE 3 k-factor (BTU in/hr ft2 ° F.) Mean Temperature (° F.) HFO-1234zeHFC-134a cyclopentane 40 0.127 0.146 0.143 75 0.142 0.163 0.153

This example demonstrates the k-factor performance of HFO-1234ze, andisomers thereof, when HFO-1234ze blowing agent is substituted into thepolyurethane formulation. HFO-1234ze was substituted in an equal molarconcentration to that of the benchmark fdams. Table 3 data illustratesthat HFO-1234ze foams k-factors are considerably better than HFC-134a orcyclopentane foams.

Example 4 Polyurethane Foam K-Factors

This example demonstrates the performance of blowing agents comprisingHFO-1234ze (including isomers thereof) in combination with various HFCco-blowing agents used in connection with the preparation ofpolyurethane foams. The same foam formulation, equipment and proceduresused in Examples 2 and 3 are used, with the exception of the blowingagent. A blowing agent is prepared comprising HFO-1234ze (includingisomers thereof) in a concentration of approximately 80 weight percentof the total blowing agent, and HFC-245fa in a concentration ofapproximately 20 weight percent of the total blowing agent. In additionto blowing agent in accordance with the present invention, HFC-134a andcyclopentane were each also tested as the blowing agent. In each system,the blowing agent was added in substantially the same molarconcentration into the polyol blend. Foams are then formed using thisblowing agent and the k-factors of the foam are measured. Table 4 belowillustrates the k-factor performance of combinations of HFO-1234ze(including isomers thereof) when used in combination with HFC co-blowingagents.

TABLE 4 k-factor (BTU in/hr ft2 ° F.) Temperature (° F.)HFC-1234ze/HFC-245fa HFC-134a cyclopentane 40 0.129 0.146 0.143 75 0.1440.163 0.153

One unexpected result illustrated by this example is the ability toprocess HFO-1234ze, and HFC-1234ze/HFC blends in conventionalpolyurethane processing equipment. This is potentially of a greatadvantage in so far that it permits foam processing with various typesof systems and equipment, including: masterbatch type blendingequipment, gaseous blowing agent blending equipment, third streamaddition of the blowing agent, or blowing agent addition at the foamhead.

Example 5 Polyurethane Foam K-Factors

This example further demonstrates the unexpected performance of blowingagents in accordance with the present invention as used in theproduction of polyurethane foams. Three appliance polyurethane foams aremade, each one being formed using substantially the same materials,procedures and equipment, with the exception that different blowingagents are used. The polyol system is a commercially available,appliance-type formulation adapted for use with a liquid blowing agent.A foam machine is used to form the foam. The blowing agents are used inessentially equal molar concentrations. After formation, each foam iscut into samples suitable for measuring k-factors, which are found to beas indicated in the following Table 5B below. The blowing agentcomposition in weight percent on the basis of total blowing agent isdisclosed in Table 5A below:

TABLE 5A Blowing Agent A B C HF0-1234ze* 85 0 60 HFC-245fa 15 100 11Cyclopentane 0 0 29 *100% cis

TABLE 5B k-factor(BTU in/hr ft² ° F.) Mean Temperature (° F.) A B C 400.116 0.119 0.116 75 0.131 0.134 0.132 110 0.146 0.149 0.148The results reported in Table 8C illustrate that the use of a compoundof the present invention (HFO-1234ze) in combination with cyclopentaneand HFC-245fa as co-blowing agents for thermoset foams at these levelsdid not impact in a deleterious manner the k-factor performance ofHFO-1234ze when used alone or with HFC-245fa. This is an unexpectedresult because heretofor the use of cyclopentane in substantial amountsin blowing agent formulations has had a deleterious impact on k-factorperformance.

Example 6 Polyurethane Foam K-Factors

A further experiment was performed using the same polyol formulation andisocyanate as in Example 5. The foam is prepared by hand mix, Theblowing agents consist of a compound in accordance with Formula II,namely, HFCO-1233zd (CF3CH═CHCl)* in about the same mole percentage ofthe foamable composition as the blowing agent in Example 5. K-factorsare found to be as indicated in Table 6 below.

TABLE 6 Mean Temperature (° F.) k-factor (BTU in/hr ft² ° F.) 40 0.12775 0.143 110 0.159

1-41. (canceled)
 42. A foamable composition comprising: (a) a foamforming agent for forming a thermal insulating foam; and (b) a lowglobal warming potential GWP blowing agent having a GWP of less thanabout 500 and comprising at least about 15% by weight of1,1,1,3-tetrafluoropropene (HFO-1234ze), said HFO-1234ze consisting oftransHFO-1234ze.
 43. The foamable composition of claim 42 wherein saidfoam forming agent comprises at least one thermoset foam component. 44.The foamable composition of claim 43 wherein said at least one thermosetcomponent comprises a composition capable of forming polyurethane foam.45. The foamable composition of claim 43 wherein said at least onethermoset component comprises a composition capable of formingpolyisocyanurate foam.
 46. The foamable composition of claim 43 whereinsaid at least one thermoset component comprises a composition capable offorming phenolic foam.
 47. The foamable composition of claim 42 whereinsaid foam forming agent comprises at least one thermoplastic foamcomponent.
 48. The foamable composition of claim 47 wherein said atleast one thermoplastic foam component comprises a thermoplasticpolymer.
 49. The foamable composition of claim 47 wherein said at leastone thermoplastic component comprises a polyolefin.
 50. The foamablecomposition of claim 49 wherein said polyolefin is selected from thegroup consisting of monovinyl aromatic compounds, ethylene-basedcompounds, propylene-based polymers, and combinations of these.
 51. Thefoamable composition of claim 49 wherein said polyolefin is selectedfrom the group consisting of polystyrene, ethylene homopolymers,polypropylene, polyethyleneterepthalate (PET) and combinations of these.52. The foamable composition of claim 47 wherein the foam forming agentis a thermoplastic and said blowing agent further comprises a compoundselected from the group consisting of C1-C5 alcohols, C1-C4 ethers, andcombinations of two or more of these.
 53. The foamable composition ofclaim 43 wherein the foam forming agent is a thermoplastic and saidblowing agent further comprises ethanol.
 54. The foamable composition ofclaim 43 wherein the foam forming agent is a thermoplastic and saidblowing agent further comprises a compound selected from the groupconsisting of dimethyl ether, diethyl ether and combinations of these.55. The foamable composition of claim 43 wherein the foam forming agentis a thermoset and said blowing agent further comprises methyl formate.56. (canceled)
 57. A method of forming a foam comprising adding to afoamable and/or foaming composition a low global warming potential GWPblowing agent having a GWP of less than about 500 and comprising atleast about 15% by weight of 1,1,1,3-tetrafluoropropene (HFO-1234ze),said HFO-1234ze consisting of transHFO-1234ze.
 58. The method of claim57 further comprising reacting the foamable composition under conditionseffective to form a cellular structure.
 59. The method of claim 57wherein said foamable composition comprises isocyanate.
 60. The methodof claim 57 wherein said foamable composition comprises polyol. 61.(canceled)
 62. A foam formed from the foamable composition of claim 42.63. An article selected from the group consisting of block, foam, andlaminate comprising the foam of claim
 62. 64. The foam of claim 62 beingin a form selected from the group consisting of rigid foam, open cellfoam, closed cell foam, flexible foam, spray foam, one component, frothsand integral skin foam.
 65. A refrigerator comprising the foam of claim62.
 66. A freezer comprising the foam of claim
 62. 67. The foam of claim62 having a k-factor K-factor (BTU in/hr ft²° F.) at 40° F. of notgreater than about 0.14. 68.-70. (canceled)